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Publication numberUS5304566 A
Publication typeGrant
Application numberUS 07/700,165
Publication dateApr 19, 1994
Filing dateOct 4, 1990
Priority dateOct 6, 1989
Fee statusPaid
Also published asUS5612358
Publication number07700165, 700165, US 5304566 A, US 5304566A, US-A-5304566, US5304566 A, US5304566A
InventorsKeiichi Ishimitsu, Junji Suzuki, Haruhito Ohishi, Tomio Yamada, Renpei Hatano, Nobuo Takakusha, Jun Mitsui
Original AssigneeNippon Soda Co., Ltd
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Pyridine compounds which have useful insecticidal utility
US 5304566 A
Abstract
The present invention relates to a compound having the formula below which has an excellent inseciticidal activity: ##STR1## wherein R1 represents an optionally substituted 5-6 membered aromatic hetero ring containing nitrogen atom, except a non-substituted 2-pyridyl; x represents an optionally substituted C1-3 alkylene
R2 represents a hydrogen, a carbamoyl, a mono or di C1-5 alkyl carbamoyl, a thiocarbamoyl, a mono or di C1-5 alkylthiocarbamoyl, a sulfamoyl, a mono or di C1-5 alkylsulfamoyl, an optionally substituted C1-5 alkyl, an optionally substituted C2-5 alkenyl, an optionally substituted C2-5 alkynyl, an optionally substituted C3-8 cycloalkyl, an optionally substituted C3-8 cycloalkenyl, an optionally substituted aryl or --Y--R5 ;
Y represents O, S(O)n, CO, CS or CO2 ;
n represents 0, 1 or 2;
R5 represents a hydrogen, an optionally substituted C1-5 alkyl, an optionally substituted C2-5 alkenyl, an optionally substituted C2-5 alkynyl, an optionally substituted C3-8 cycloalkyl, an optionally substituted C3-8 cycloalkenyl or an optionally substituted aryl;
R3 represents a hydrogen, an optionally substituted C1-5 alkyl, an optionally substituted C2-5 alkenyl, an optionally substituted C2-5 alkynyl, an optionally substituted C3-8 cycloalkyl or an optionally substituted C3-8 cycloalkenyl; R4 represents a cyano or a nitro; and Z represents CH or N; or its salt.
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Claims(16)
We claim:
1. An insecticidal compound of the formula ##STR269## wherein A completes a 5 or 6 membered aromatic ring having one heteroatomic ring member comprising nitrogen, provided, however, that the ring is not unsubstituted 2-pyridyl;
R1 is hydrogen or C1-5 alkyl; C1-5 haloalkyl, C1-5 alkoxy, C1-5 alkylthio, C1-5 alkylsulfonyl, cyano, halogen, or C1-5 dialkylamino;
X is C1-3 alkylene or C1-3 alkylidene;
R2 is hydrogen, carbamoyl, monoalkylcarbamoyl, C1-5 dialkylcarbamoyl, thiocarbamoyl, monoalkylthiocarbamoyl, sulfamoyl, monoalkylsulfamoyl, C1-5 dialkylsulfamoyl, C1-5 alkyl, C2-5 alkenyl, C2-5 alkynyl, C3-8 cycloalkyl, C3-8 cycloalkenyl, aryl, or the radical
--Y--R5 
wherein
Y is 0, S(O)n, CO, CS or CO2, n is 0, 1 or 2,
R5 is hydrogen, C1-5 alkyl, C2-5 alkenyl, C2-5 alkynyl, C3-8 cycloalkyl, C3-8 cycloalkenyl, or aryl;
R3 is hydrogen, C1-5 alkyl, C2-5 alkenyl, C2-5 alkynyl, C3-8 cycloalkyl, or C3-8 cycloalkenyl;
R4 is cyano or nitro;
Z is CH or N;
and an insecticidal acceptable salt thereof.
2. An insecticidal compound according to claim 1 wherein the aromatic ring is of the formula ##STR270## wherein A completes a 6 membered aromatic ring selected from the group pyridyl;
R1 is hydrogen or C1-5 alkyl; C1-5 haloalkyl, C1-5 alkoxy, C1-5 alkylthio, C1-5 alkylsulfonyl, cyano, halogen, or C1-5 dialkylamino;
X is C1-3 alkylene or C1-3 alkylidene;
R2 is hydrogen, monoalkylcarbamoyl, C1-5 dialkylcarbamoyl, C1-5 alkyl, C2-5 alkenyl, C2-5 alkynyl, C3-6 cycloalkyl, aryl, or the radical
--Y--R5 
wherein
Y is O, CO, CO2 or SO2 ;
R5 is C1-5 alkyl or aryl;
R3 is hydrogen, C1-5 alkyl, or C3-6 cycloalkyl;
Z is N;
and an insecticidal acceptable salt thereof.
3. N-cyano-N'-(2-chloro-5-pyridylmethyl)-N'-methylacetamidine.
4. 2-(2-chloro-5-pyridylmethylamino)-1-nitro-1-butene.
5. N-cyano-N'-(2-chloro-5-pyridylmethyl)-N'-ethylacetamidine.
6. N-(2-chloro-5-pyridylmethyl)-N-methyl-N'-nitroacetamidine.
7. An insecticidal composition comprising the compound of claim 2 as an active ingredient.
8. An insecticidal composition comprising the compound of claim 3 as an active ingredient.
9. An insecticidal composition comprising the compound of claim 4 as an active ingredient.
10. An insecticidal composition comprising the compound of claim 5 as an active ingredient.
11. Method of controlling both lepidopterous and hemipterous insects by applying to the locus where control is desired an insecticidally effective amount of a compound of claim 1.
12. Method of controlling both lepidopterous and hemipterous insects by applying to the locus where control is desired an insecticidally effective amount of a compound of claim 2.
13. Method of controlling both lepidopterous and hemipterous insects by applying to the locus where control is desired an insecticidally effective amount of the compound of claim 3.
14. Method of controlling both lepidopterous and hemipterous insects by applying to the locus where control is desired an insecticidally effective amount of the compound of claim 4.
15. Method of controlling both lepidopterous and hemipterous insects by applying to the locus where control is desired an insecticidally effective amount of the compound of claim 5.
16. Method of controlling both lepidopterous and hemipterous insects by applying to the locus where control is desired an insecticidally effective amount of the compound of claim 6.
Description
FIELD OF INVENTION

The present invention relates to new amine derivatives, the processes for the production thereof and insecticides containing the said derivatives as effective compounds.

DESCRIPTION OF RELATED ART

A large number of chemicals, for example, organophosphorus compounds such as parathion and malathion and carbamate compounds such as carbaryl and methomyl, have been developed and put to practical use as insecticides over many years. These insecticides have played a very great role for the improvement of agricultural production. However, in recent years some of these insecticides are regulated on their use because of problems such as environmental pollution due to residue or accumulation, or cause infestation of resistant insect pests as a result of long-term use. Therefore, there is a need to develop new chemicals which have excellent insecticidal characteristics over various types of insect pests including these resistant insect pests and which can be used safely.

The following compound is known as the isomer compound of this invention, which has no insecticidal activity. ##STR2## Further, the following compound is described in U.S. Pat. No. 4,918,088, which has insecticidal activities. ##STR3## The compound however shows no insecticidal activity against lepidopterous insects and green rice leafhopper which are more serious pests on crops, though it shows some activity against cotton aphid.

The purpose of this invention is to provide agricultural chemicals which can be advantageously synthesized industrially, have certain effects and may be applied safely.

The compound of this invention has high insecticidal activity against both lepidopterous and hemipterous insects.

SUMMARY OF THE INVENTION

The present invention relates to a compound having the formula ##STR4## wherein R1 represents an optionally substituted 5-6 membered aromatic hetero ring containing nitrogen atom, except a nonsubstituted 2-pyridyl;

X represents an optionally substituted C1-3 alkylene or alkylidene;

R2 represents a hydrogen, a carbamoyl, a mono or di C1-5 alkyl carbamoyl, a thiocarbamoyl, a mono or di C1-5 alkylthiocarbamoyl, a sulfamoyl, a mono or di C1-5 alkylsulfamoyl, an optionally substituted C1-5 alkyl, an optionally substituted C2-5 alkenyl, an optionally substituted C2-5 alkynyl, an optionally substituted C3-8 cycloalkyl, an optionally substituted C3-8 cycloalkenyl, an optionally substituted aryl or --Y--R5 ;

Y represents O, S(O)n, CO, CS or CO2 ;

n represents 0, 1 or 2;

R5 represents a hydrogen, an optionally substituted C1-5 alkyl, an optionally substituted C2-5 alkenyl, an optionally substituted C2-5 alkynyl, an optionally substituted C3-8 cycloalkyl, an optionally substituted C3-8 cycloalkenyl or an optionally substituted aryl;

R3 represents a hydrogen, an optionally substituted C1-5 alkyl, an optionally substituted C2-5 alkenyl, an optionally substituted C2-5 alkynyl, an optionally substituted C3-8 cycloalkyl or an optionally substituted C3-8 cycloalkenyl;

R4 represents a cyano or a nitro; and Z represents CH or N; or its salt.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The compounds of this invention can be prepared in accordance with the following reaction schemes:

(1) Preparation Method 1: ##STR5## where r1 and r2 represent a C1-5 alkyl; and R1, R2, R3, R4 and X are as defined above.

The reaction is carried out in an inactive organic solvent, preferably in an aromatic hydrocarbon solvent such as xylene, toluene or benzene, in the presence of acidic catalyst such as p-toluenesulfonic acid, if necessary, under reflux.

(2) Preparation method 2: ##STR6## where r3 represents a C1-5 alkyl: and R1, R2, R3 and X are as defined above. This reaction is carried out in an inactive organic solvent, preferably in an alcohol such as methanol, ethanol, between room temperature and the boiling point of the used solvent.

(3) Preparation Method 3: ##STR7## where Hal represents a halogen; and R1, R2, R3 and X are as defined above. This reaction is carried out in an inactive organic solvent, preferably DMF, THF, benzene acetonitrile, acetone, methylethylketone, in the presence of acid accepter such as potassium carbonate, NaH, triethylamine, between room temperature and the boiling point of the used solvent.

(4) Preparation Method 4: ##STR8## where R1, R2, R3, X and Hal are as defined above. This reaction is carried out in the same manner as that of Preparation Method 3.

(5) Preparation Method 5: ##STR9## where R1, R2, R3 and X are as defined above. This reaction is carried out in an inactive organic solvent, preferably acetonitrile, carbon tetrachloride, dichloroethane, in the presence of nitration reagent such as nitronium tetrafluoroborate, between -20 C. and the boiling point of the used solvent.

After the reaction is completed, an usual after-treatment gives the intended compound. The structure of the compounds of this invention was determined by such means as IR, NMR, MASS, etc. When R2 is hydrogen in a compound of this invention, tautomers represented by ##STR10## can exist.

The syn-aniti isomers, when Z represents N, and the cis-trans isomers, when Z represents CH, as represented by, ##STR11## can also exist.

The ratio varies depending on e.g. conditions of instrumental analysis.

The following EXAMPLES illustrate the present invention.

EXAMPLE 1 2-(2-chloro-5-pyridylmethylamino)-1-nitro-1-butene ##STR12##

In 50 ml of toluene, 4.2 g of 2-chloro-5-pyridylmethylamine, 3.5 g of 1-nitro-2-butanone and 0.1 g of p-toluene sulfonic acid were mixed and the mixture was refluxed for 2 hours. The solvent was then distilled off and the residue was purified by column chromatography on silica gel to afford 4.1 g of compound No. 368. m.p. 95-98 C.

EXAMPLE 2 2-(2-chloro-5-pyridylmethylamino)-1-cyano-1-propene ##STR13##

1.4 g of 2-chloro-5-pyridylmethylamine and 0.8 g of 1-cyano-2-propanone were mixed and the mixture was stirred at room temperature over night. The solvent was then distilled off and the residue was purified by column chromatography on silica gel to afford 1.7 g of compound No. 528. m.p. 95-98 C.

EXAMPLE 3 N-cyano-N'-(2-chloro-5-pyridylmethyl)-N'-methylacetamidine ##STR14##

In 20 ml of ethanol, 1.6 g of N-methyl-2-cloro-5-pyridylmethylamine and 1.2 g of ethyl-N-cyanoacetamidine were mixed and the mixture was stirred at room temperature over night. The solvent was then distilled off and the residue was purified by column chromatography on silica gel to afford 1.8 g of compound No. 22. m.p. 101-103 C.

EXAMPLE 4 N-cyano-N'-(2-chloro-5-pyridylmethyl)-N'-ethylacetamidine ##STR15##

0.7 g of sodium hydride (purity 60%) was added to the solution of 3.0 g of N-cyano-N'-(2-chloro-5-pyridylmethyl)acetamidine in 20 ml of N.N-dimethylformamide at ice bath temperature. After stirring it at the same temperature for 1 hour, 2.7 g of ethyl iodide was added to the mixture, followed by stirring for 5 hours at room temperature. The reaction mixture was then poured into ice-water, extracted with ethyl acetate, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue obtained was purified by column chromatography on silica gel to afford 1.6 g of compound No. 51. m.p. 100-101 C.

EXAMPLE 5 N-cyano-N-(2-chloro-5-pyridylmethyl)-N'-methylacetamidine ##STR16##

0.6 g of sodium hydride (purity 60%) was added to the solution of 1.3 g of N-cyano-N'-methylacetamidine in 20 ml of N,N-dimethylformamide at ice bath temperature. After stirring it at the same temperature for 1 hour, 2.2 g of 2-chloro-5-pyridylmethylchloride was added to the mixture, followed by stirring for 5 hours at room temperature. The reaction mixture was then poured into ice-water, extracted with ethyl acetate, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue obtained was purified by column chromatography on silica gel to afford 1.5 g of compound No. 22 m.p. 101-103 C.

REFERENCE EXAMPLE N-(2-chloro-5-pyridylmethyl)-N-methylacetamidine hydrochloride ##STR17##

To 40 ml of ethanol was added 5.1 g of N-(2-chloro-5-pyridylmethyl)-N-Methylamine and then 4 g of ethyl acetimidate hydrochloride at 0 C. After stirring for an hour, the reaction mixture was allowed to warm to room temperature and stirred over night. The solvent was then distilled off. The obtained white residue was washed with diethyl ether to afford 7.3 g of the title compound m.p. 192-197 C.

EXAMPLE 6 N-(2-chloro-5-pyridylmethyl)-N-methyl-N'-nitroacetamidine ##STR18##

To a suspension of 1 g of N-(2-chloro-5-pyridylmethyl)-N-methylamidine hydrochloride in 10 ml of dry acetonitrile was added dropwise 0.7 g of DBU under nitrogen at room temperature. After stirring for 30 minutes, the solution was added dropwise to a suspension of 0.6 g of nitronium tetrafluoroborate in 5 ml of dry acetonitrile under nitrogen on cooling with ice-water and let stir for 4 hours. After which time, the mixture was poured into ice-water, then extracted several time with chloroform. The combined chloroform layer was dried over magnesium sulfate, filtered and distilled off. The crude oil was purified by column chromatgraphy on silica gel to afford 0.3 g of compound No. 236.

ND 25 1.5808.

Typical examples of this invention including those described above are listed in Table 1.

                                  TABLE 1__________________________________________________________________________ poundCom-##STR19##                                             [ ]pertiesPro-P                                                     hysicalNo.   R1 X         R2      R3           Z  R4                                                     m.p.__________________________________________________________________________                                                     C. 1    ##STR20##        H            H                 N  CN [123-126] 2 "                 "            CH3          "  "  [141-143] 3 "                 "            CH2 Cl       "  "  [124-126] 4 "                 "            CH2 F        "  "  [151-152] 5 "                 "            CF3          "  "  [112-114] 6 "                 "            C2 H5   "  "  [120-122] 7 "                 "            C3 H7 (n)                                               "  "  [100-101] 8 "                 "                              ##STR21##        "  "  [193.5- 195] 9 "                 "            C4 H9 (t)                                               "  " 10   "                 "            CH2 OCH3                                               "  "  [128-                                                     128.5] 11   "                 "            CH2 SCH3                                               "  "  [116-118] 12    ##STR22##        H            CH2 COOC2 H5                                               N  CN nD 25.5                                                      1.5608 13   "                 "            CH2 CH2 COOC2 H5                                               "  " 14   "                 "            CH2 NHCH3                                               "  " 15   "                 "            CH2 N(CH3)2                                               "  " 16   "                 "            CH2 CH2 CH2 Cl                                               "  "  [114-115] 17   "                 "                              ##STR23##        "  "  [190-191] 18   "                 "            CH2 CN       "  "  [106-108] 19   "                 "            CH2 CH2 CN                                               "  " 20   "                 "                              ##STR24##        "  "  [187-189] 21   "                 CH3     H                 "  "  nD 25                                                     1.5918 22   "                 "            CH3          "  "  [101-103] 23   "                 "            "                 "  "  [161-162]                                                     HCl salt 24   "                 "            CH2 Cl       "  "  nD 26.5                                                     .                                                     1.5921 25   "                 "            CH2 F        "  "  [79-80] 26   "                 "            CF3          "  "  *1 27    ##STR25##        CH3     C2 H5   N  CN nD 27                                                     1.5742 28   "                 "            C3 H7 (n)                                               "  "  [97-100] 29   "                 "                              ##STR26##        "  "  nD 24.5                                                      1.5829 30   "                 "            C4 H9 (t)                                               "  " 31   "                 "            CH2 OCH3                                               "  "  nD 24                                                     1.5803 32   "                 "            CH2 SCH3                                               "  "  nD 24.5                                                     1.6070 33   "                 "            CH2 COOC2 H5                                               "  "  nD 25.5                                                     1.5604 34   "                 "            CH2 CH.sub. 2 COOC2 H5                                               "  "  nD 24.5                                                     1.5605 35   "                 "            CH2 NHCH3                                               "  "  nD 25                                                     1.5861 36   "                 "            CH2 N(CH3)2                                               "  "  nD 25                                                     1.5577 37   "                 "            CH2 CH2 Cl                                               "  " 38   "                 "            CH2 CH2 CH2 Cl                                               "  "  nD 25.5                                                     1.5830 39   "                 "                              ##STR27##        "  " 40   "                 "                              ##STR28##        "  " 41   "                 "                              ##STR29##        "  "  nD 25.5                                                      1.6040 42    ##STR30##        CH3     CHCH.sub. 2       N  CN 43   "                 "            CH2 CN       "  "  nD 25                                                     1.5913 44   "                 "            CH2 CH2 CN                                               "  "  [112-114] 45   "                 "                              ##STR31##        "  " 46   "                 "                              ##STR32##        "  "  [224-226] 47   "                 CHF2    H                 "  " 48   "                 "            CH3          "  "  nD 24.5                                                     1.5423 49   "                 "            C2 H5   "  " 50   "                 C2 H5                             H                 "  "  [101-103] 51   "                 "            CH3          "  "  [100-101] 52   "                 "            C.sub. 2 H5  "  " 53   "                 C3 H7 (i)                             H                 "  "  [205-207] 54   "                 "            CH3          "  " 55   "                 "            C2 H5   "  " 56   "                 ##STR33##   H                 "  " 57    ##STR34##                 ##STR35##   CH3          N  CN nD 25                                                     1.5825 58   "                 "            C2 H5   "  " 59   "                 CH2 OCH3                             H                 "  " 60   "                 "            CH3          "  "  nD 25.5                                                     1.5711 61   "                 CH2 SCH3                             H                 "  " 62   "                 "            CH3          "  "  nD 25                                                     1.5828 63   "                 CH2 COOC2 H5                             H                 "  " 64   "                 "            CH3          "  "  nD 25                                                     1.5475 65   "                 ##STR36##   H                 "  " 66   "                 "            CH3          "  "  nD 25.5                                                     1.5928 67   "                 ##STR37##   H                 "  " 68   "                 "            CH3          "  "  nD 25.5                                                     1.6155 69   "                 ##STR38##   H                 "  " 70   "                 "            CH3          "  "  nD 24.5                                                     1.6093 71   "                 ##STR39##   H                 "  " 72    ##STR40##                 ##STR41##   CH3          N  CN [112-114] 73   "                 CH2 CHCH2                             H                 "  "  nD 25                                                     1.5841 74   "                 "            CH3          "  "  nD 25                                                     1.5809 75   "                 CH2 CCH H                 "  " 76   "                 "            CH3          "  "  nD 25.5                                                     1.5730 77   "                 CH2 CN  H                 "  " 78   "                 "            CH3          "  "  [127-128] 79   "                 ##STR42##   H                 "  " 80   "                 "            CH3          "  "  [124-127] 81   "                 ##STR43##   H                 "  " 82   "                 "            CH3          "  "  nD 24.5                                                     1.6045 83   "                 ##STR44##   H                 "  " 84   "                 "            CH3          "  "  nD 25.5                                                     1.6092 85   "                 ##STR45##   H                 "  " 86    ##STR46##                 ##STR47##   CH3          N  CN nD 25.5                                                      1.5910 87   "                 ##STR48##   H                 "  " 88   "                 "            CH3          "  "  nD 25.5                                                     1.6162 89   "                 ##STR49##   H                 "  " 90   "                 "            CH.sub. 3         "  "  [115-117] 91   "                 OCH3    H                 "  " 92   "                 "            CH3          "  "  [110-112] 93   "                 CHO          H                 "  " 94   "                 "            CH3          "  " 95   COCH3        H            "                 "  "  nD 25.5                                                     1.5475 96   "                 "            CH3          "  "  [84-86] 97   "                 SO2 CH3                             H                 "  "  [160-163] 98   "                 "            CH3          "  " 99   "                 ##STR50##   H                 "  "100   "                 "            CH3          "  "  [112-114]101    ##STR51##        COOC2 H5                             H                 N  CN102   "                 "            CH3          "  "  nD 25                                                     1.5540103   "                 CONH2   H                 "  "104   "                 "            CH3          "  "105   "                 ##STR52##   H                 "  "106   "                 "            CH3          "  "  [89-91]107   "                 CONHCH3 H                 "  "108   "                 "            CH3          "  "109   "                 CSNHCH3 H                 "  "110   "                 "            CH3          "  "111    ##STR53##        H            CH3          "  "112   "                 CH3     "                 "  "113    ##STR54##        H            "                 "  "114   "                 CH3     "                 "  "115    ##STR55##        H            "                 "  "  [83-85]116    ##STR56##        CH3     CH3          N  CN [76-78]117    ##STR57##        H            "                 "  "118   "                 CH3     "                 "  "  [145-147]119    ##STR58##        H            "                 "  "120   "                 CH3     "                 "  "  nD 25                                                     1.5202121    ##STR59##        H            "                 "  "122   "                 CH3     "                 "  "123    ##STR60##        H            "                 "  "124   "                 CH3     "                 "  "  nD 25.5                                                     1.5580125    ##STR61##        H            "                 "  "126   "                 CH3     "                 "  "127    ##STR62##        H            "                 "  "128   "                 CH3     "                 "  "129    ##STR63##        H            "                 "  "  [162-163]130   "                 CH3     "                 "  "  [105-107]131    ##STR64##        H            CH3          N  CN132   "                 CH3     "                 "  "  [138-139]133    ##STR65##        H            "                 "  "134   "                 CH3     "                 "  "  nD 25                                                     1.5841135    ##STR66##        H            "                 "  "136   "                 CH3     "                 "  "  [107-109]137    ##STR67##        H            "                 "  "138   "                 CH3     "                 "  "139    ##STR68##        H            "                 "  "140   "                 CH3     "                 "  "141    ##STR69##        H            "                 "  "142   "                 CH3     "                 "  "143    ##STR70##        H            "                 "  "  [122-124]144   "                 CH3     "                 "  "  [110-113]145    ##STR71##        H            CH3          N  CN [66-68]146   "                 CH3     "                 "  "  nD 24.5                                                     1.5790147    ##STR72##        H            "                 "  "148   "                 CH3     "                 "  "  [94-96]149    ##STR73##        H            "                 "  "  [130-132]150   "                 CH3     "                 "  "  nD.sup.                                                     25                                                     1.5612151    ##STR74##        H            "                 "  "  [96-99]152   "                 CH3     "                 "  "  nD 25.5                                                     1.5800153    ##STR75##        H            "                 "  "154   "                 CH3     "                 "  "155    ##STR76##        H            "                 "  "156    ##STR77##        CH3     CH3          N  CN157    ##STR78##        H            "                 "  "158   "                 CH3     "                 "  "159    ##STR79##        H            "                 "  "160   "                 CH3     "                 "  "161    ##STR80##        H            "                 "  "162   "                 CH3     "                 "  "163    ##STR81##        H            "                 "  "  [115-117]164   "                 CH3     "                 "  "  nD 23                                                     1.5717165    ##STR82##        H            "                 "  "  [104-106]166   "                 CH3     "                 "  "167    ##STR83##        H            CH3          N  CN168   "                 CH3     "                 "  "169    ##STR84##        H            "                 "  "  [112-114]170   "                 CH3     "                 "  "  nD 25                                                     1.5413171    ##STR85##        H            "                 "  "  [122-124]172   "                 CH3     "                 "  "  [143-144]173   "                 "            C2 H5   "  "  nD 25                                                     1.5575174   "                 C2 H5                             CH3          "  "  [63-70]175    ##STR86##        H            "                 "  "  [149-151]176   "                 CH3     "                 "  "177    ##STR87##        H            H                 "  "  [179-183]178   "                 CH3     "                 "  "  nD 25                                                     1.5952179    ##STR88##        H            CH3          N  CN180   "                 CH3     "                 "  "181    ##STR89##        H            "                 "  "182   "                 CH3     "                 "  "183    ##STR90##        H            "                 "  "184   "                 CH3     "                 "  "185    ##STR91##        H            "                 "  "186   "                 CH3     "                 "  "187    ##STR92##        H            "                 "  "188   "                 CH3     "                 "  "  [106-109]189    ##STR93##        H            CH3          "  "  [90-92]190    ##STR94##        CH3     CH3          N  CN [102-103]191    ##STR95##        H            "                 "  "192   "                 CH3     "                 "  "193    ##STR96##        H            H                 "  "194   "                 "            CH3          "  "  [127-129]195   "                 "            CH2 Cl       "  "196   "                 "            CH2 F        "  "197   "                 "            C2 H5   "  "198   "                 "                              ##STR97##        "  "199   "                 "            CH2 SCH3                                               "  "200   "                 "            CH2 OCH3                                               "  "201    ##STR98##        H            C3 H7 (n)                                               N  CN nD 25.5                                                      1.5528202   "                 CH3     H                 "  "203   "                 "            CH3          "  "  nD 25.5                                                     1.5798204   "                 "            CH2 Cl       "  "205   "                 "            CH2 F        "  "206   "                 H            C2 H5   "  "  nD 25.5                                                     1.5657207   "                 "                              ##STR99##        "  "208   "                 "            CH2 SCH3                                               "  "209   "                 "            CH2 OCH3                                               "  "210   "                 "            C3 H7 (i)                                               "  "211   "                 "            C4 H9 (t)                                               "  "212    ##STR100##       C2 H5                             H                 N  CN213   "                 "            CH3          "  "  nD 24.5                                                     1.5665214   "                 "            CH2 Cl       "  "215   "                 "            C2 H5   "  "216   "                 C3 H7 (i)                             H                 "  "217   "                 "            CH3          "  "218   "                 "            C2 H5   "  "219   "                 COCH3   H                 "  "220   "                 "            CH3          "  "221   "                 SO2 CH3                             H                 "  "222   "                 "            CH3          "  "223    ##STR101##       H            H                 N  NO2224   "                 "            CH3          "  "225   "                 "            CH2 Cl       "  "226   "                 "            CH2 F        "  "227   "                 "            C2 H5   "  "228   "                 "                              ##STR102##       "  "229   "                 "            CH2 SCH3                                               "  "230   "                 "            CH2 OCH3                                               "  "231   "                 "            C3 H7 (i)                                               "  "232   "                 "            C4 H9 (t)                                               "  "233   "                 "            CHCH2        "  "234   "                 "                              ##STR103##       "  "235    ##STR104##       CH3     H                 N  NO2236   "                 "            CH3          "  "  nD 25                                                     1.5808237   "                 "            CH2 Cl       "  "238   "                 "            CH2 F        "  "239   "                 "            C2 H5   "  "240   "                 "                              ##STR105##       "  "241   "                 "            CH2 SCH3                                               "  "242   "                 "            CH2 OCH3                                               "  "243   "                 "            C3 H7 (n)                                               "  "244   "                 "            C4 H9 (t)                                               "  "245   "                 "            CHCH2        "  "246   "                 "                              ##STR106##       "  "247    ##STR107##       C2 H5                             H                 N  NO2248   "                 "            CH3          "  "249   "                 "            C2 H5   "  "250   "                 C3 H7 (i)                             H                 "  "251   "                 "            CH3          "  "252   "                 "            C2 H5   "  "253   "                 ##STR108##  H                 "  "254   "                 "            CH3          "  "255   "                 "            C2 H5   "  "256   "                 COCH3   H                 "  "257   "                 "            CH3          "  "258   "                 SO2 CH3                             H                 "  "259   "                 "            CH3          "  "260    ##STR109##       H            CH3          N  NO2261   "                 CH3     "                 "  "262    ##STR110##       H            "                 "  "263   "                 CH3     "                 "  "264    ##STR111##       H            "                 "  "265   "                 CH3     "                 "  "266    ##STR112##       H            "                 "  "267   "                 CH3     "                 "  "268    ##STR113##       H            "                 "  "269   "                 CH3     "                 "  "270    ##STR114##       H            "                 "  "271   "                 CH3     "                 "  "272    ##STR115##       H            CH3          N  NO2273   "                 CH3     "                 "  "274    ##STR116##       H            "                 "  "275   "                 CH3     "                 "  "276    ##STR117##       H            "                 "  "277   "                 CH3     "                 "  "278    ##STR118##       H            "                 "  "279   "                 CH3     "                 "  "280    ##STR119##       H            "                 "  "281   "                 CH3     "                 "  "282    ##STR120##       H            "                 "  "283   "                 CH3     "                 "  "284    ##STR121##       H            CH3          N  NO2285   "                 CH3     "                 "  "286    ##STR122##       H            "                 "  "287   "                 CH3     "                 "  "288    ##STR123##       H            "                 "  "289   "                 CH3     "                 "  "290    ##STR124##       H            "                 "  "291   "                 CH3     "                 "  "292    ##STR125##       H            "                 "  "293   "                 CH3     "                 "  "294    ##STR126##       H            CH3          N  NO2295   "                 CH3     "                 "  "296    ##STR127##       H            "                 "  "297   "                 CH3     "                 "  "298    ##STR128##       H            "                 "  "299   "                 CH3     "                 "  "300    ##STR129##       H            "                 "  "301   "                 CH3     "                 "  "302    ##STR130##       H            "                 "  "303   "                 CH3     "                 "  "304    ##STR131##       H            "                 "  "305    ##STR132##       CH3     CH3          N  NO2306    ##STR133##       H            "                 "  "307   "                 CH3     "                 "  "308    ##STR134##       H            "                 "  "309   "                 CH3     "                 "  "310    ##STR135##       H            "                 "  "311   "                 CH3     "                 "  "312    ##STR136##       H            "                 "  "313   "                 CH3     "                 "  "314    ##STR137##       H            CH3          N  NO2315   "                 CH3     "                 "  "316    ##STR138##       H            "                 "  "317   "                 CH3     "                 "  "318    ##STR139##       H            "                 "  "319   "                 CH3     "                 "  "320   "                 "            C2 H5   "  "321   "                 C2 H5                             CH3          "  "322    ##STR140##       H            "                 "  "323   "                 CH3     "                 "  "324    ##STR141##       H            CH3          N  NO2325   "                 CH3     "                 "  "326    ##STR142##       H            "                 "  "327   "                 CH3     "                 "  "328    ##STR143##       H            "                 "  "329   "                 CH3     "                 "  "330    ##STR144##       H            "                 "  "331   "                 CH3     "                 "  "332    ##STR145##       H            "                 "  "333   "                 CH3     "                 "  "334    ##STR146##       H            "                 "  "335   "                 CH3     "                 "  "336    ##STR147##       H            H                 N  NO2337   "                 "            CH3          "  "338   "                 "            C2 H5   "  "339   "                 "            CH2 Cl       "  "340   "                 "            CH2 F        "  "341   "                 "                              ##STR148##       "  "342   "                 "            CH2 SCH3                                               "  "343   "                 "            CH2 OCH3                                               "  "344    ##STR149##       CH3     H                 N  NO2345   "                 "            CH3          "  "346   "                 "            CH2 Cl       "  "347   "                 "            CH2 F        "  "348   "                 "            C2 H5   "  "349   "                 "                              ##STR150##       "  "350   "                 "            CH2 SCH3                                               "  "351   "                 "            CH2 OCH3                                               "  "352   "                 "            C3 H7 (i)                                               "  "353   "                 "            C4 H9 (t)                                               "  "354    ##STR151##       C2 H5                             H                 N  NO2355   "                 "            CH3          "  "356   "                 "            CH2 Cl       "  "357   "                 "            C2 H5   "  "358   "                 C3 H7 (i)                             H                 "  "359   "                 "            CH3          "  "360   "                 "            C2 H5   "  "361   "                 COCH3   H                 "  "362   "                 "            CH3          "  "363   "                 SO2 CH3                             H                 "  "364   "                 "            CH3          "  "365    ##STR152##       H            H                 CH NO2                                                     [116-118]366   "                 "            CH3          "  "  [133-135]367   "                 "            CH2 Cl       "  "368   "                 "            C2 H5   "  "  [95-98]369   "                 "            C3 H7 (i)                                               "  "  [150-152]370   "                 "            C4 H7 (t)                                               "  "371   "                 "            CHCH2        "  "372   "                 "            CHCHCH3      "  "373   "                 "            CH2 CN       "  "374   "                 "            CH2 NO2 "  "375   "                 "            CH2 COOC2 H5                                               "  "376    ##STR153##       H                              ##STR154##       CH NO2377   "                 "                              ##STR155##       "  "378   "                 "                              ##STR156##       "  "379   "                 "                              ##STR157##       "  "380   "                 CH3     H                 "  "381   "                 "            CH3          "  "  [79-82]382   "                 "            CH2 Cl       "  "383   "                 "            C2 H5   "  "  [101-104]384   "                 "            C3 H7 (i)                                               "  "385   "                 "            C4 H7 (t)                                               "  "386   "                 "            CHCH2        "  "387   "                 "            CHCHCH3      "  "388    ##STR158##       CH3     CH2 CN       CH NO2389   "                 "            CH2 NO2 "  "390   "                 "            CH2 COOC2 H5                                               "  "391   "                 "                              ##STR159##       "  "392   "                 "                              ##STR160##       "  "393   "                 "                              ##STR161##       "  "394   "                 "                              ##STR162##       "  "395   "                 C2 H5                             H                 "  "396   "                 "            CH3          "  "397   "                 "            C2 H5   "  "398   "                 C3 H7 (i)                             H                 "  "399   "                 "            CH3          "  "400    ##STR163##       C3 H7 (i)                             C2 H5   CH NO2401   "                 ##STR164##  H                 "  "402   "                 "            CH3          "  "403   "                 "            C2 H5   "  "404   "                 CH2 CHCH2                             H                 "  "405   "                 "            CH3          "  "406   "                 "            C2 H5   "  "407   "                 ##STR165##  H                 "  "408   "                 "            CH3          "  "409   "                 "            C2 H5   "  "410   "                 CHO          H                 "  "411   "                 "            CH3          "  "412    ##STR166##       CHO          C2 H5   CH NO2413   "                 COCH3   H                 "  "414   "                 "            CH3          "  "415   "                 "            C2 H5   "  "416   "                 SO2 CH3                             H                 "  "417   "                 "            CH3          "  "418   "                 "            C2 H5   "  "419   "                 COOC2 H5                             H                 "  "420   "                 "            CH3          "  "421   "                 "            C2 H5   "  "422   "                 OC2 H5                             H                 "  "423   "                 "            CH3          "  "424   "                 "            C2 H5   "  "425   "                 CH2 CCH H                 "  "426   "                 "            CH3          "  "427   "                 "            C2 H5   "  "428    ##STR167##       H            CH3          CH NO2429   "                 CH3     "                 "  "430    ##STR168##       H            "                 "  "431   "                 CH3     "                 "  "432    ##STR169##       H            "                 "  "433   "                 CH3     "                 "  "434    ##STR170##       H            "                 "  "435   "                 CH3     "                 "  "436    ##STR171##       H            "                 "  "437   "                 CH3     "                 "  "438    ##STR172##       H            "                 "  "439   "                 CH3     "                 "  "440    ##STR173##       H            CH3          CH NO2441   "                 CH3     "                 "  "442    ##STR174##       H            "                 "  "443   "                 CH3     "                 "  "444    ##STR175##       H            "                 "  "445   "                 CH3     "                 "  "446    ##STR176##       H            "                 "  "447   "                 CH3     "                 "  "448    ##STR177##       H            "                 "  "449   "                 CH3     "                 "  "450    ##STR178##       H            "                 "  "451   "                 CH3     "                 "  "452    ##STR179##       H            CH3          CH NO2453   "                 CH3     "                 "  "454    ##STR180##       H            "                 "  "455   "                 CH3     "                 "  "456    ##STR181##       H            "                 "  "457   "                 CH3     "                 "  "458    ##STR182##       H            "                 "  "459   "                 CH3     "                 "  "460    ##STR183##       H            "                 "  "461   "                 CH3     "                 "  "462    ##STR184##       H            CH3          CH NO2463   "                 CH3     "                 "  "464    ##STR185##       H            "                 "  "465   "                 CH3     "                 "  "466    ##STR186##       H            "                 "  "467   "                 CH3     "                 "  "468    ##STR187##       H            "                 "  "469   "                 CH3     "                 "  "470    ##STR188##       H            "                 "  "471   "                 CH3     "                 "  "472    ##STR189##       H            "                 "  "473    ##STR190##       CH3     CH3          CH NO2474    ##STR191##       H            "                 "  "475   "                 CH3     "                 "  "476    ##STR192##       H            "                 "  "477   "                 CH3     "                 "  "478    ##STR193##       H            "                 "  "479   "                 CH3     "                 "  "480    ##STR194##       H            "                 "  "481   "                 CH3     "                 "  "482    ##STR195##       H            "                 "  "483   "                 CH3     "                 "  "484    ##STR196##       H            CH3          CH NO2485   "                 CH3     "                 "  "486    ##STR197##       H            "                 "  "487   "                 CH3     "                 "  "488   "                 "            C2 H5   "  "489   "                 C2 H5                             CH3          "  "490    ##STR198##       H            "                 "  "491   "                 CH3     "                 "  "492    ##STR199##       H            "                 "  "493   "                 CH3     "                 "  "494    ##STR200##       H            "                 "  "495   "                 CH3     "                 "  "496    ##STR201##       H            CH3          CH NO2497   "                 CH3     "                 "  "498    ##STR202##       H            "                 "  "499   "                 CH3     "                 "  "500    ##STR203##       H            "                 "  "501   "                 CH3     "                 "  "502    ##STR204##       H            H                 CH NO2503   "                 "            CH3          "  "504   "                 "            CH2 Cl       "  "505   "                 "            C2 H5   "  "506   "                 "            C3 H7 (i)                                               "  "507   "                 "            C4 H9 (t)                                               "  "508   "                 CH3     H                 "  "509   "                 "            CH3          "  "510   "                 "            CH2 Cl       "  "511   "                 "            C2 H5   "  "512   "                 "                              ##STR205##       "  "513    ##STR206##       CH3     C3 H7 (i)                                               CH NO2514   "                 "            C4 H9 (t)                                               "  "515   "                 C2 H5                             H                 "  "516   "                 "            CH3          "  "517   "                 "            C2 H5   "  "518   "                 ##STR207##  H                 "  "519   "                 "            CH3          "  "520   "                 "            C2 H5   "  "521   "                 COCH3   H                 "  "522   "                 "            CH3          "  "523   "                 "            C2 H5   "  "524   "                 SO2 CH3                             H                 "  "525   "                 "            CH3          "  "526   "                 "            C2 H5   "  "527    ##STR208##       H            H                 CH CN528   "                 "            CH3          "  "  [95-98]529   "                 "            CH2 Cl       "  "530   "                 "            C2 H5   "  "531   "                 "            C3 H7 (i)                                               "  "532   "                 "            C4 H9 (t)                                               "  "533   "                 "            CHCH2        "  "534   "                 "            CHCHCH3      "  "535   "                 "            CH2 CN       "  "536   "                 "            CH2 NO2 "  "537   "                 "            CH2 COOC2 H5                                               "  "538    ##STR209##       H                              ##STR210##       CH CN539   "                 "                              ##STR211##       "  "540   "                 "                              ##STR212##       "  "541   "                 "                              ##STR213##       "  "542   "                 CH3     H                 "  "543   "                 "            CH3          "  "  nD 29                                                     1.5941544   "                 "            CH2 Cl       "  "545   "                 "            C2 H5   "  "546   "                 "            C3 H7 (i)                                               "  "547   "                 "            C4 H9 (t)                                               "  "548   "                 "            CHCH2        "  "549   "                 "            CHCHCH3      "  "550    ##STR214##       CH3     CH2 CN       CH CN551   "                 "            CH2 NO2 "  "552   "                 "            CH2 COOC2 H5                                               "  "553   "                 "                              ##STR215##       "  "554   "                 "                              ##STR216##       "  "555   "                 "                              ##STR217##       "  "556   "                 "                              ##STR218##       "  "557   "                 C2 H5                             H                 "  "558   "                 "            CH3          "  "559   "                 "            C2 H5   "  "560   "                 C3 H7 (i)                             H                 "  "561   "                 "            CH3          "  "562    ##STR219##       C3 H7 (i)                             C2 H5   CH CN563   "                 ##STR220##  H                 "  "564   "                 "            CH3          "  "565   "                 "            C2 H5   "  "566   "                 CH2 CHCH2                             H                 "  "567   "                 "            CH3          "  "568   "                 "            C2 H5   "  "569   "                 ##STR221##  H                 "  "570   "                 "            CH3          "  "571   "                 "            C2 H5   "  "572   "                 CHO          H                 "  "573   "                 "            CH3          "  "574    ##STR222##       CHO          C2 H5   CH CN575   "                 COCH3   H                 "  "576   "                 "            CH3          "  "577   "                 "            C2 H5   "  "578   "                 SO.sub. 2 CH3                             H                 "  "579   "                 "            CH3          "  "580   "                 "            C2 H5   "  "581   "                 COOC2 H5                             H                 "  "582   "                 "            CH3          "  "583   "                 "            C2 H5   "  "584   "                 OC2 H5                             H                 "  "585   "                 "            CH3          "  "586   "                 "            C2 H5   "  "587   "                 CH2 CCH H                 "  "588   "                 "            CH3          "  "589   "                 "            C2 H5   "  "590    ##STR223##       H            CH3          CH CN591   "                 CH3     "                 "  "592    ##STR224##       H            "                 "  "593   "                 CH3     "                 "  "594    ##STR225##       H            "                 "  "595   "                 CH3     "                 "  "596    ##STR226##       H            "                 "  "597   "                 CH3     "                 "  "598    ##STR227##       H            "                 "  "599   "                 CH3     "                 "  "600    ##STR228##       H            "                 "  "601   "                 CH3     "                 "  "602    ##STR229##       H            CH3          CH CN603   "                 CH3     "                 "  "604    ##STR230##       H            "                 "  "605   "                 CH3     "                 "  "606    ##STR231##       H            "                 "  "607   "                 CH3     "                 "  "608    ##STR232##       H            "                 "  "609   "                 CH3     "                 "  "610    ##STR233##       H            "                 "  "611   "                 CH3     "                 "  "612    ##STR234##       H            "                 "  "613   "                 CH3     "                 "  "614    ##STR235##       H            CH3          CH CN615   "                 CH3     "                 "  "616    ##STR236##       H            "                 "  "617   "                 CH3     "                 "  "618    ##STR237##       H            "                 "  "619   "                 CH3     "                 "  "620    ##STR238##       H            "                 "  "621   "                 CH3     "                 "  "622    ##STR239##       H            "                 "  "623   "                 CH3     "                 "  "624    ##STR240##       H            CH3          CH CN625   "                 CH3     "                 "  "626    ##STR241##       H            "                 "  "627   "                 CH3     "                 "  "628    ##STR242##       H            "                 "  "629   "                 CH3     "                 "  "630    ##STR243##       H            "                 "  "631   "                 CH3     "                 "  "632    ##STR244##       H            "                 "  "633   "                 CH3     "                 "  "634    ##STR245##       H            "                 "  "635    ##STR246##       CH3     CH3          CH CN636    ##STR247##       H            "                 "  "637   "                 CH3     "                 "  "638    ##STR248##       H            "                 "  "639   "                 CH3     "                 "  "640    ##STR249##       H            "                 "  "641   "                 CH3     "                 "  "642    ##STR250##       H            "                 "  "643   "                 CH3     "                 "  "644    ##STR251##       H            CH3          CH CN645   "                 CH3     "                 "  "646    ##STR252##       H            "                 "  "647   "                 CH3     "                 "  "648    ##STR253##       H            "                 "  "649   "                 CH3     "                 "  "650   "                 "            C2 H5   "  "651   "                 C2 H5                             CH3          "  "652    ##STR254##       H            CH3          CH CN653   "                 CH3     "                 "  "654    ##STR255##       H            "                 "  "655   "                 CH3     "                 "  "656    ##STR256##       H            "                 "  "657   "                 CH3     "                 "  "658    ##STR257##       H            "                 "  "659   "                 CH3     "                 "  "660    ##STR258##       H            "                 "  "661   "                 CH3     "                 "  "662    ##STR259##       H            "                 "  "663   "                 CH3     "                 "  "664    ##STR260##       H            H                 CH CN665   "                 "            CH3          "  "666   "                 "            CH2 Cl       "  "667   "                 "            C2 H5   "  "668   "                 "            C3 H7 (i)                                               "  "669   "                 "            C4 H9 (t)                                               "  "670   "                 CH3     H                 "  "671   "                 "            CH3          "  "672   "                 "            CH2 Cl       "  "673   "                 "            C2 H5   "  "674   "                 "                              ##STR261##       "  "675    ##STR262##       CH3     C3 H7 (i)                                               CH CN676   "                 "            C4 H9 (t)                                               "  "677   "                 C2 H5                             H                 "  "678   "                 "            CH3          "  "679   "                 "            C2 H5   "  "680   "                 ##STR263##  H                 "  "681   "                 "            CH3          "  "682   "                 "            C2 H5   "  "683   "                 COCH3   H                 "  "684   "                 "            CH3          "  "685   "                 "            C2 H5   "  "686   "                 SO2 CH3                             H                 "  "687    ##STR264##       SO2 CH3                             CH3          CH CN688   "                 "            C2 H5   "  "__________________________________________________________________________ *1 1 HNMR(CDCl3) δ; ppm 3.32(s, 3H), 4.63(s, 2H), 7.37(d, 1H), 7.62(dd, 1H), 8.37(d, 1H)

The compounds of this invention exhibit high insecticidal activities against various species of insect pests such as cutworms, diamondback moth, aphids, leafhoppers and planthoppers. In recent years the decrease of the control effects of organophosphorus and carbamate insecticides, which is caused by the development of resistance to these insecticides, has become serious problem. In such situations, the development of new insecticides which is effective on the resistant pests has been desired. The compounds of this invention possess superior insecticidal activities against not only susceptible strains but also resistant ones.

The insecticides covered by this invention contain as active ingredients one or more types of the compounds as expressed by the general formula (1). These active ingredients, may be used as produced but normally they are used in any of the forms which ordinary agricultural chemicals can take, namely wettable powder, dust, emulsifiable concentrate, suspension concentrates, smoking chemicals, fumigant, granule, or other formulations. For additives and carriers are used soybean flour, wheat flour or other vegetable flours, diatomaceous earth, apatite, gypsum, talc, pyrophyllite, clay or other fine mineral powders, when solid formulations are intended.

When liquid formulations are intended, then for solvents are used kerosene, mineral oil, petroleum, solvent naphtha, xylene, cyclohexane, cyclohexanone, dimethylformamide, dimethylsulfoxide, alcohol, acetone, water, etc. A surface active agent may, if necessary, be added in order to give a homogeneous and suitable formulation. The wettable powders, emulsifiable concentrates, suspension concentrates, etc. thus obtained are diluted with water into suspensions or emulsions of a prescribed concentration, before they are actually sprayed on plants in the field. In the case of dusts or granules, they are directly applied without further processing.

It goes without saying that the compound(s) of this invention is effective even alone, but it can be used by mixing with various types of insecticides, acaricides and fungicides.

Typical examples of acaricides and insecticides which can be used by mixing with the compounds of this invention are described below:

Acaricides (fungicides): chlorobenzilate, chloropropylate, proclonol, bromopropylate, dicofol, dinobuton, binapacryl, chlordimeform, amitraz, propargite, PPPS, benzoximate, hexythiazox, fenbutatin oxide, polynactine, chinomethionat, thioquinox, chlorfenson, tetradifon, phenproxide, avermectins, clofentezine, flubenzimine, fenazaquin, pyridaben, fenproximate, chlorfenethol, thiophanate-methyl, benomyl, thiram, iprobenfos, edifenfos, fthalide, probenazole, isoprothiolane, chorothalonil, captan, polyoxin-B, blasticidin-S, kasugamycin, validamycin, tricyclazole, pyroquilon, phenazine oxide, mepronil, flutolanil, pencycuron, iprodione, hymexazole, metalaxyl, triflumizole, diclomezine, tecloftalam, vinclozolin, procymidone, bitertanol, triadimefon, prochloraz, pyrifenox, fenarimal, fenpropimorph, triforine, metalaxyl, oxycarboxin, pefrazoate, diclomedine, fluazinam, oxadixyl, ethoquinolac, TPTH, propamocarb, fosetyl, dihydrostreptomycin, anilazine, dithianon, diethofencarb. Organophosphorus-type and carbamate-type insecticides (acaridides): fenthion, fenitrothion, diazinon, chlorpyrifos, oxydeprofos, vamidothion, phenthoate, dimethoate, formothion, malathion, trichlorfon, thiometon, phosmet, menazon, dichlorvos, acephate, EPBP, dialifos, parathion-methyl, oxydemeton-methyl, ethion, aldicarb, propoxur, methomyl, fenobucarb, BPMC, pyraclofos, monocrotophos, salithion, cartap, carbosulfan carbofuran, benfuracarb, metolcarb, carbaryl, pirimicarb, ethiofencarb, fenoxycarb,

Pyrethroide-type insecticides (acaricides): permethrin, cypermethrin, deltamethrin, fenvalerate, fenpropathrin, pyrethrins, allethrin, tetramethrin, resmethrin, parthrin, dimethrin, proparthrin, bifenthrin, prothrin, fluvalinate, cyfluthrin, cyhalothrin, flucythrinate, ethofenprox, cycloprothrin, tralomethrin, silaneophan. Benzoylphenylurea-type and other types insecticides: diflubenzuron, chlorfluazuron, triflumuron, teflubenzuron, buprofezin, pyriproxyfen, flufenoxuron, Machine oil.

Same examples of the formulations are given below. The carriers, surface-active agents, etc. that are added, however, are not limited to these Examples.

EXAMPLE 7 Emulsifiable concentrate

______________________________________The compound of this invention                 10 partsAlkylphenyl polyoxyethylene                  5 partsDimethyl formamide    50 partsXylene                35 parts______________________________________

These components are mixed and dissolved and, for use in spraying, the liquid mixture is water-diluted into an emulsion.

EXAMPLE 8 Wettable powder

______________________________________The compound of this invention                 20 partsHigher alcohol sulfuric ester                  5 partsDiatomaceous earth    70 partsSilica                 5 parts______________________________________

These components are mixed and ground to fine powder, which for use in spraying, are water-diluted into a suspension.

EXAMPLE 9 Dust

______________________________________The compound of this invention                    5 partsTalc                     94.7 partsSilica                   0.3 parts______________________________________

These are mixed and ground and used as-ground in spraying.

EXAMPLE 10 Granule

______________________________________The compound of this invention                     5 partsClay                     73 partsBentonite                20 paratsSodium dioctylsulfosuccinate                     1 partSodium phosphate          1 part______________________________________

The above compounds are granulated, and applied as it is when used.

Industrial applicability

The tests below show the insecticidal activity of the compounds of this invention.

TEST 1 Efficacy for cotton aphid

30 to 50 insects of cotton aphid per plot were inoculated using a small brush on cucumber leaves which were seeded in pots, 10 cm in diameter, and 10 days old after germination. A day later, wounded insect pests were removed, and a chemical solution, which was prepared in the way that the emulsifiable concentrate described in Example 7 of the above example of insecticide was diluted with water to 125 ppm of compound concentration according to the prescription, was sprayed. The pots were placed in a thermostatic room at temperature of 25 C. and humidity of 65%. The number of survival pests was counted 7 days later and the control efficacy was calculated by comparing with that of untreated plot. The results are shown in Table 2.

              TABLE 2______________________________________                Control Efficacy (7 days later)Compound No.   125 ppm______________________________________ 1              100% 2             100 3             100 4             100 6             100 8             100 10            100 16            100 20            100 21            100 22            100 23            100 24            100 25            100 27            100 29            100 31            100 32            100 33            100 38            100 44            100 48            100 50            100 51            100 53            100 57            100 60            100 62            100 64            100 66            100 68            100 70            100 72            100 73            100 74            100 78            100 80            100 82            100 84            100 86            100 88            100 92            100 96            100100            100102            100115            100116            100120            100124            100130            100132            100136            100144            100145            100146            100148            100149            100150            100151            100152            100163            100164            100169            100170            100171            100172            100173            100174            100177            100178            100188            100189            100190            100194            100203            100206            100213            100236            100366            100368            100381            100383            100543            100Comparative compound A           27Comparative compound B          100______________________________________ Comparative compound A: ##STR265## Comparative compound B: ##STR266##
TEST 2 Efficacy for green rice leafhopper

Rice seedlings of 7 days old after germination were immersed in a chemical solution, which was prepared in the way that the emulsifiable concentrate described in Example 7 of the above example of insecticide was diluted with water to 125 ppm of compound concentration according to prescription, for 30 seconds. After dried in air, the treated seedlings were placed in test tubes and 10 insects of 3rd-instar larvae of green rice leafhopper resistant to the organophosphorus and carbamate insecticides were inoculated. The tubes were covered with gauze, and placed in a thermostatic room at temperature of 25 C. and humidity of 65%. The mortality was checked 5 days later. The results are shown in Table 3.

              TABLE 3______________________________________                 % mortality (5 days later)Compound No.     125 ppm______________________________________ 1                 100% 2                100 4                100 6                100 8                10010                10016                10018                10020                10021                10022                10023                10024                10025                10027                10028                10029                10031                10032                10033                10035                10036                10044                10048                10050                10051                10053                10057                10060                10062                10066                10068                10072                10073                10074                10078                10082                10084                10086                10088                10092                10096                100100               100102               100116               100120               100124               100130               100132               100136               100144               100146               100148               100150               100152               100164               100169               100170               100171               100172               100173               100174               100178               100188               100190               100201               100203               100213               100236               100366               100368               100369               100381               100Comparative Compound A              0Comparative Compound B              0Comparative Compound C              0______________________________________ Comparative compound A and B: The same as test 1 Compound C: ##STR267##
TEST 3 Efficacy for rice armyworm

The test compounds were formulated into the wettable powder in the same manner as Example 8. The compounds were diluted with water to 125 ppm. A maize leaf was immersed in the chemical solution for 30 seconds. After air-dried, the treated leaf was placed in a petri dish and five 3rd-instar larvae of rice armyworm were inoculated. The petri dishes were covered with glass lids, and placed in a thermostatic room at 25 C. and 65% relative humidity. The mortality was checked 5 days later. Two replications were conducted in the each test. The results are shown in Table 4.

              TABLE 3______________________________________                 % mortality (5 days later)Compound No.     125 ppm______________________________________21                 100%22                10023                10024                10025                10051                10057                10088                10092                100148               100172               100381               100Comparative compound A              0Comparative compound B              0Comparative compound D              40______________________________________ Comparative compound A and B: The same as Test 1 Compound D: ##STR268##
Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US4918088 *Jul 13, 1988Apr 17, 1990Ciba-Geigy CorporationAcarina
Non-Patent Citations
Reference
1 *Chemical Abstracts, vol. 115 (9), Abstract No. 92.085a, p. 745, Sep. 2, 1991.
2 *Del Corona et al, Boll. Chim. Farm , vol. 118 (11), pp. 661 666 (1979).
3Del Corona et al, Boll. Chim. Farm, vol. 118 (11), pp. 661-666 (1979).
4 *Hackh s Chemical Dictionary, p. 62, 1969.
5Hackh's Chemical Dictionary, p. 62, 1969.
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Classifications
U.S. Classification514/357, 546/286, 514/344, 514/352, 546/311, 546/329, 514/345, 546/338, 546/300, 546/334, 546/332
International ClassificationC07D213/57, C07D277/32, C07D213/643, C07D241/16, C07D405/12, C07D213/70, C07D213/84, A01N47/40, C07D237/08, C07D237/12, C07D241/12, C07D277/30, C07D213/64, C07D417/12, C07D213/74, C07D239/26, C07D213/61, C07D409/12, A01N43/40, C07D231/12, A01N51/00
Cooperative ClassificationC07D237/08, C07D417/12, C07D237/12, C07D405/12, C07D241/12, C07D213/643, C07D241/16, C07D213/61, A01N51/00, C07D213/70, C07D213/74, C07D213/57, A01N43/40, A01N47/40, C07D277/30, C07D231/12, C07D213/64, C07D239/26, C07D409/12, C07D213/84, C07D277/32
European ClassificationC07D237/08, A01N51/00, C07D241/16, A01N47/40, A01N43/40, C07D213/57, C07D213/61, C07D277/30, C07D237/12, C07D213/64, C07D213/74, C07D213/70, C07D231/12, C07D213/84, C07D213/643, C07D239/26, C07D241/12, C07D277/32, C07D409/12, C07D405/12, C07D417/12
Legal Events
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May 16, 1991ASAssignment
Owner name: NIPPON SODA CO., LTD.D A CORPORATION OF JAPAN, JA
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